The binder, a critical electrode component, significantly influences lithium‐ion batteries (LIB) performance, yet remains an under‐researched area. The widespread use of polyvinylidene fluoride (PVDF) as a commercial binder is challenged by its surging cost, attributed to limited production and increased demand, highlighting the necessity for alternatives. Here, we synthesize poly (trifluoroethyl methacrylate) (PTFEMA), a polymer with a molecular weight in the million range, through a straightforward radical solution polymerization method, aiming to use it as a cathode binder for LIBs. PTFEMA demonstrate good stability across the typical operating temperatures and voltages, along with robust adhesion to the current collector. Moreover, the PTFEMA outperforms PVDF in terms of electrolyte affinity and lithium‐ion conductivity, thereby achieving capacity and stability comparable to those of its PVDF counterparts. This investigation confirms the homopolymer form of PTFEMA as a compelling alternative to PVDF, representing a valuable exploration of binder technology for LIBs.